CN101514393B - Dearsenization method for sulfurous iron ore slag - Google Patents
Dearsenization method for sulfurous iron ore slag Download PDFInfo
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- CN101514393B CN101514393B CN2008102334317A CN200810233431A CN101514393B CN 101514393 B CN101514393 B CN 101514393B CN 2008102334317 A CN2008102334317 A CN 2008102334317A CN 200810233431 A CN200810233431 A CN 200810233431A CN 101514393 B CN101514393 B CN 101514393B
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Abstract
本发明是硫铁矿烧渣的一种脱砷工艺，该工艺是将硫铁矿烧渣用硫酸水溶液在20～50℃的温度下，搅拌处理0.5～2.5小时，然后经分离、洗涤得到砷含量小于0.07％的精制硫铁矿烧渣，脱砷率为96～98％；该工艺具有处理过程简单，处理时间短，操作容易，砷去除率高等特点。由于该发明生产设备成本低，性能优异，因此具有很强的市场竞争能力和推广应用价值。The present invention is a process for removing arsenic from pyrite slag. The process is to process pyrite slag with sulfuric acid aqueous solution at a temperature of 20-50°C for 0.5-2.5 hours, and then separate and wash to obtain arsenic. The refined pyrite slag with content less than 0.07% has arsenic removal rate of 96-98%. The process has the characteristics of simple treatment process, short treatment time, easy operation and high arsenic removal rate. Because the production equipment of the invention has low cost and excellent performance, it has strong market competitiveness and popularization and application value.
Description
技术领域technical field
本发明属化工行业中固体废弃物处理的领域，具体为涉及硫铁矿烧渣中砷的脱出方法。The invention belongs to the field of solid waste treatment in the chemical industry, and specifically relates to a method for removing arsenic from pyrite slag.
背景技术Background technique
硫铁矿烧渣是硫铁矿煅烧生产硫酸时产出的固体废弃物，每年约产出1500万吨，占整个化工废渣的1/3，主要元素成分是铁，通常经适当处理如磁选等即可达到炼铁的原料要求而用作炼铁原料，但由于硫铁矿烧渣中同时含有砷、铜、锌、铅等对炼铁不利的杂质元素，从而使其应用受到限制。对硫铁矿烧渣进行脱砷处理，通过降低烧渣中的砷含量，使其达到炼铁的原料质量要求，不仅可以弥补我国铁资源的不足，同时可消除硫铁矿烧渣对生态环境的污染，具有明显的经济效益与社会效益。Pyrite slag is the solid waste produced when pyrite is calcined to produce sulfuric acid. The annual output is about 15 million tons, accounting for 1/3 of the entire chemical waste slag. The main element is iron. It is usually treated properly such as magnetic separation It can meet the raw material requirements of ironmaking and can be used as ironmaking raw material, but because pyrite slag contains arsenic, copper, zinc, lead and other impurity elements that are unfavorable to ironmaking, its application is limited. The arsenic removal treatment of pyrite slag can reduce the arsenic content in the slag and make it meet the quality requirements of ironmaking raw materials, which can not only make up for the shortage of iron resources in my country, but also eliminate the impact of pyrite slag on the ecological environment. The pollution has obvious economic and social benefits.
固体物料中砷的脱除方法主要有火法工艺和湿法工艺两类：There are mainly two types of arsenic removal methods in solid materials: fire process and wet process:
火法工艺脱砷是指在高温炉中通过氧化还原反应使砷生成三氧化二砷的形式挥发脱出，或通过加碱焙烧、水浸出脱砷，或通过加入酸性弱于砷酸的弱酸盐焙烧、水浸出脱砷，这种方法具有方法筒便、设备简单、成本低、无环境污染等优点，适用于高砷固体物料的脱砷处理，但该类方法能耗较高，脱砷深度有限。Dearsenization by pyrotechnics refers to volatilization of arsenic into diarsenic trioxide through oxidation-reduction reaction in high temperature furnace, or dearsenization by adding alkali roasting, water leaching, or adding weak salt acid weaker than arsenic acid roasting, water Leaching for arsenic removal, this method has the advantages of convenient method, simple equipment, low cost, and no environmental pollution. It is suitable for the removal of arsenic from high-arsenic solid materials, but this type of method consumes a lot of energy and the depth of arsenic removal is limited.
湿法工艺脱砷是指采用含有脱砷处理剂的水溶液在温度100℃以内的条件下处理，使砷以砷酸或亚砷酸的形式进入溶液，从而与固体物料分离。使用的脱砷处理剂包括铁氧化物、过氧化氢、过氧乙酸、含锰氧化物、含氯氧化物、或它们的混合物，氢氧化钠等，这类方法具有操作过程简单、反应温和、砷脱除率高、能耗低的特点。The wet process for arsenic removal refers to the use of an aqueous solution containing arsenic removal treatment agent at a temperature of less than 100°C, so that arsenic enters the solution in the form of arsenic acid or arsenous acid, thereby separating it from the solid material. The arsenic removal treatment agent used includes iron oxide, hydrogen peroxide, peracetic acid, manganese-containing oxide, chlorine-containing oxide, or their mixture, sodium hydroxide, etc. This type of method has the advantages of simple operation process, mild reaction, It has the characteristics of high arsenic removal rate and low energy consumption.
发明内容Contents of the invention
本发明的目的在于提供一种工艺流程简单，处理时间短，操作容易、安全、脱砷率高的脱出硫铁矿烧渣砷的新方法。The purpose of the present invention is to provide a new method for removing arsenic from pyrite slag with simple process flow, short processing time, easy and safe operation and high arsenic removal rate.
本发明一种硫铁矿烧渣中砷的脱出方法的特征是:将硫铁矿烧渣置入酸性水溶液中，加热，搅拌反应，然后经分离、洗涤、抽滤烘干得到低砷含量的精制硫铁矿烧渣。A method for extracting arsenic from pyrite slag of the present invention is characterized in that: pyrite slag is placed in an acidic aqueous solution, heated, stirred and reacted, and then separated, washed, suction filtered and dried to obtain arsenic with low arsenic content Refined pyrite cinder.
所述的硫铁矿烧渣是指工业上采用硫铁矿煅烧生产硫酸时产出的固体废渣。The pyrite slag refers to the solid waste produced when pyrite is calcined to produce sulfuric acid in industry.
所述的硫铁矿烧渣是指含砷大于1.5％，含铁在55％以上的经选矿后得到硫铁矿烧渣。The pyrite slag refers to the pyrite slag which contains more than 1.5% arsenic and more than 55% iron and is obtained after mineral processing.
所述的酸性溶液为硫酸溶液。The acidic solution is a sulfuric acid solution.
所述的加热温度为20～80℃，酸性水溶液中硫酸的浓度为5～30％。The heating temperature is 20-80 DEG C, and the sulfuric acid concentration in the acidic aqueous solution is 5-30%.
所述的搅拌反应时间0.5～2.5小时，搅拌速度为200～500转/分。The stirring reaction time is 0.5-2.5 hours, and the stirring speed is 200-500 rpm.
所述的硫铁矿烧渣：水溶液的重量百分比为1：2.5～10。The weight percentage of the pyrite slag:water solution is 1:2.5-10.
所述的洗涤为采用一般的自来水进行洗涤。Described washing is to adopt common tap water to wash.
本发明是这样实现的：将硫铁矿烧渣放入已升温至20～80℃、含硫酸5～30％的水溶液中，硫铁矿烧渣和水溶液的比例为1：2.5～1:10，恒温搅拌反应0.5～2.5小时，搅拌速度为200～500转/分，反应结束后，冷却至室温，待硫铁矿烧渣溶液静止分层后，进行固液分离。分离后的硫铁矿烧渣，再加自来水洗涤，清洗至中性为止，然后抽滤烘干即得到精制的硫铁矿烧渣。本发明是硫铁矿烧渣的一种脱砷工艺，该工艺是将硫铁矿烧渣用酸水溶液在加热下，搅拌处理，然后经分离、洗涤得到砷含 量小于0.07％的精制硫铁矿烧渣，脱砷率为96～98％。The present invention is realized in the following way: put the pyrite slag into the aqueous solution which has been heated to 20-80°C and contains 5-30% sulfuric acid, and the ratio of the pyrite slag to the aqueous solution is 1:2.5-1:10 , stirring and reacting at constant temperature for 0.5-2.5 hours, the stirring speed is 200-500 rpm, after the reaction is completed, cool to room temperature, and separate the solid and liquid after the pyrite slag solution is static and stratified. The separated pyrite slag is washed with tap water until it is neutral, and then filtered and dried to obtain refined pyrite slag. The present invention is a process for removing arsenic from pyrite slag. The process is to process the pyrite slag with acid solution under heating, stirring, and then separate and wash to obtain refined pyrite with arsenic content less than 0.07%. Mine slag, arsenic removal rate of 96 to 98%.
具体实施方式Detailed ways
实施例1：在烧杯中加入含硫酸15％的硫酸水溶液500克，升温至50℃后，加入硫铁矿烧渣150克，恒温搅拌反应1.5小时，搅拌速度为250转/分，冷却至室温，静止分层，过滤、洗涤、抽滤烘干即得到精制硫铁矿烧渣，该样品经分析，硫铁矿烧渣中砷含量为0.072％，精制硫铁矿烧渣铁含量为60.23％。Example 1: Add 500 grams of sulfuric acid aqueous solution containing 15% sulfuric acid in a beaker, heat up to 50°C, add 150 grams of pyrite slag, stir and react at a constant temperature for 1.5 hours, the stirring speed is 250 rpm, and cool to room temperature , static layering, filtration, washing, suction filtration and drying to obtain refined pyrite slag. After analysis of the sample, the arsenic content in pyrite slag is 0.072%, and the iron content in refined pyrite slag is 60.23%. .
实施例2：在烧杯中加入含硫酸15％的硫酸水溶液500克，升温至80℃后，加入硫铁矿烧渣150克，恒温搅拌反应2.5小时，搅拌速度为250转/分，冷却至室温，静止分层，过滤、洗涤、抽滤烘干即得到精制硫铁矿烧渣，该样品经分析，硫铁矿烧渣中砷含量为0.070％，精制硫铁矿烧渣铁含量为60.75％。Example 2: Add 500 grams of sulfuric acid aqueous solution containing 15% sulfuric acid in a beaker, heat up to 80°C, add 150 grams of pyrite slag, stir and react at a constant temperature for 2.5 hours, the stirring speed is 250 rpm, and cool to room temperature , static stratification, filtration, washing, suction filtration and drying to obtain refined pyrite slag. After analysis of the sample, the arsenic content in the pyrite slag is 0.070%, and the iron content in the refined pyrite slag is 60.75%. .
实施例3：在烧杯中加入含硫酸15％的硫酸水溶液500克，升温至20℃后，加入硫铁矿烧渣150克，恒温搅拌反应2.5小时，搅拌速度为400转/分，冷却至室温，静止分层，过滤、洗涤、抽滤烘干即得到精制硫铁矿烧渣，该样品经分析，硫铁矿烧渣中砷含量为0.049％，精制硫铁矿烧渣铁含量为62.23％。Example 3: Add 500 grams of sulfuric acid aqueous solution containing 15% sulfuric acid in a beaker, heat up to 20°C, add 150 grams of pyrite slag, stir and react at a constant temperature for 2.5 hours, the stirring speed is 400 rpm, and cool to room temperature , static layering, filtration, washing, suction filtration and drying to obtain refined pyrite slag. After analysis of the sample, the arsenic content in pyrite slag is 0.049%, and the iron content in refined pyrite slag is 62.23%. .
实施例4：在烧杯中加入含硫酸15％的硫酸水溶液500克，升温至30℃后，加入硫铁矿烧渣150克，恒温搅拌反应2.5小时，搅拌速度为500转/分，冷却至室温，静止分层，过滤、洗涤、抽滤烘干即得到精制硫铁矿烧渣，该样品经分析，硫铁矿烧渣中砷含量为0.045％，精制硫铁矿烧渣铁含量为61.86％。Example 4: Add 500 grams of sulfuric acid aqueous solution containing 15% sulfuric acid in a beaker, heat up to 30°C, add 150 grams of pyrite slag, stir and react at a constant temperature for 2.5 hours, the stirring speed is 500 rpm, and cool to room temperature , static layering, filtration, washing, suction filtration and drying to obtain refined pyrite slag. After analysis of the sample, the arsenic content in pyrite slag is 0.045%, and the iron content in refined pyrite slag is 61.86%. .
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| CN102534197B (en) * | 2012-02-09 | 2014-04-30 | 昆明川金诺化工股份有限公司 | Method utilizing sulfuric acid roasting slag to prepare fine iron powder |
| CN103088203B (en) * | 2013-03-01 | 2015-08-12 | 罗涛 | Method for producing iron concentrate powder by using sulfuric acid residues |
| CN103572041A (en) * | 2013-10-25 | 2014-02-12 | 湖南省环境保护科学研究院 | Wet deep dearsenification method for high-arsenic iron ores |
| CN105541064B (en) * | 2016-01-21 | 2019-02-19 | 昆明理工大学 | A kind of combined disposal method of heavy metal sludge and polluted acid |
| CN115849456B (en) * | 2022-12-14 | 2024-07-26 | 湖北虹润高科新材料有限公司 | Method for preparing ferric oxide by using pyrite cinder and application thereof |
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| CN1676637A (en) * | 2004-03-31 | 2005-10-05 | 郁南县广鑫冶炼有限公司 | Non-polluting arsenic-alkali slag treatment technology |
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| CN1676637A (en) * | 2004-03-31 | 2005-10-05 | 郁南县广鑫冶炼有限公司 | Non-polluting arsenic-alkali slag treatment technology |
Non-Patent Citations (2)
| Title |
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| 李亚军等.化学法脱硫铁矿烧渣砷的研究.化工科技 4.2008,(4),33～35. |
| 李亚军等.化学法脱硫铁矿烧渣砷的研究.化工科技 4.2008,(4),33～35. * |
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